JPH08283369A - Production of halogen-free polyurethane/polyurea having flame resistance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a process for the production of flame resistant, halogen-free polyurethanes/polyureas with improved properties.

SOLUTION: In the process for the production of a flame resistant, halogen- free from a polyisocyanate and a polyol comprising adding an amine adduct of an acidic metal salt of the formula: A_1-3B_0-12P_3-9N_4-12M_0-9xH₂O (I) (wherein A is at least one hydroxide or oxide of a metal selected from the group consisting of aluminum, magnesium calcium and zinc; B is orthoboric acid; P is an acid containing phosphorus; N is at least one of an amine and ammonia; M is an alkali metal hydroxide; and x is an integer of 0-90) to the mixture of the polyisocyanate and the polyol, an aqueous solution of at least one sugar or a polymethylol compound is further added to said mixture.

COPYRIGHT: (C)1996,JPO

Description

Detailed Description of the Invention

The present invention relates to a process for the production of flame-resistant halogen-free polyurethane / polyureas with improved properties.

Additives containing halogen compounds and / or soluble phosphorus compounds for improving the behavior of polyurethanes / polyureas are very effective, but have potential toxicity, are often hydrolyzed and are comparable. Is expensive. Therefore, efforts must be made to eliminate such drawbacks.

Halogen-free inorganic fillers such as metal phosphates are also very effective as burn-preventing additives. However, due to their inability to participate in the progression of chemical reactions during the production of polyurethane / polyurea, such fillers do not disperse uniformly as can be readily seen by microscopic examination, leading to deterioration of mechanical properties (brittleness). Induced).

Proposal in the conventional method (Patent application 0
8 / 424,678 and German Patent Specification P44
38 409), polyurethane / polyureas are prepared using aqueous compositions of amine adducts of acidic metal salts during the manufacturing process. In these adducts, the polyurethane / polyurea capacity contributes to the progress of chemical reactions during production and the resulting products contain these adducts in a uniform distribution. For example, these adducts are uniformly mixed into the cell wall.
In this way it is possible to produce polyurethane / polyureas which are tough, tough and have the properties of rigid foams.

The water introduced with the production of the adduct does not adversely affect the formation of the foam. Even a light and stable foamed product with a uniform fine cell structure is obtained when using less polyisocyanate than is necessary to bind water with the polyisocyanate by the reaction.

Polyurethanes / polyureas prepared with aqueous compositions of amine adducts of metal acid salts generally have all the tests (DIN 410) required to enter fire classification B2.
Pass 2). However, it does not pass the so-called combustion shaft test. In this test, a chimney-shaped shaft is made from the test material and a gas flame is applied to it from below. After being flamed for a period of time, the test material should not continue to burn and the degree of damage should be to a certain height.

In the present invention, a mixture of polyisocyanate and polyol has the formula A _1-3 B _0-12 P _3-9 N _4-12 M _0-9 xH ₂ O (I) where A is aluminum, magnesium, Represents at least one hydroxide or oxide of a metal selected from the group consisting of calcium and zinc, B represents orthoboric acid, P represents an acid containing phosphorus, N represents at least one of amine or ammonia. , M represents an alkali metal hydroxide, x represents an integer of 0 to 90, and an amine adduct of an acidic metal salt is added, and a flame-free polyurethane having flame resistance from polyisocyanate and polyol is added. / Process for producing polyurea, an improved process has been found which is characterized in that an aqueous solution of at least one sugar or polymethylol compound is further added to the mixture. Was issued.

The polyurethane / polyurea produced according to the present invention preferably has a cell structure. A particular embodiment of the process according to the invention is further characterized in that urea is used. The addition of urea surprisingly reduces the viscosity of the aqueous composition of the amine adduct of the acidic metal salt.
This improves operability and gives excellent results in the combustion shaft test.

According to the invention, more than 5% by weight of amine adducts of acidic metal salts and more than 0.5% by weight of sugar and / or polymethylol compounds are added, and optionally by the addition of urea, the density is increased. For example, 15-500g /
1 polyurethane / polyurea foam can be obtained.

[0010] Suitable amine adducts of acidic metal salts of formula (I) are those of formula _{(II) A 2~3 B 3~9 P} 6 N 6~9 M 0~5 xH 2 O (II) . Here, each symbol has the meaning defined in the formula (I).

In formulas (I) and (II), P preferably represents orthophosphoric acid, methylphosphonic acid, pyrophosphoric acid, oligophosphoric acid and / or polyphosphoric acid. In formulas (I) and (II), A preferably means aluminum hydroxide, P is preferably orthophosphoric acid, N is preferably an alkanolamine, such as a lower alkanolamine, especially mono-, di- and / or Or triethanolamine, M is preferably sodium or potassium hydroxide, and x is preferably an integer of 6 to 36. N particularly preferably represents monoethanolamine.

Suitable amine adducts of acidic metal salts, their aqueous compositions and their preparation are described, for example, in US Pat.
No. 814, No. 5,053,148, No. 5,18
No. 2,049, and No. 5,425,901, and patent applications 08 / 149,424 and 08 during the application.
/ 424,678 and German Patent Publication No. 4
2 26 044 and 44 38 409.2
No.

Suitable amine adducts of acidic metal salts are, for example, acidic aluminum phosphates of 20 to 1 in aqueous medium.
Stir at 20 ° C. to a final pH of 5,425,901-8.
It is most easily obtained by mixing with an alkanolamine or an orthoboric acid adduct of an alkanolamine while keeping it at 5, preferably 6 to 7.0.

The aqueous composition of the amine adduct of the acidic metal salt preferably contains less than 50% by weight of water,
Particularly preferably, it contains 20 to 45% by weight of water.

Aqueous solutions of sugars which can be used are, for example, the aqueous solutions of conventional sugars and sugar-like compounds. The sugar can also be, for example, triose, tetrose, pentose, and carbohydrates, such as soluble starch, dextrin, dextran, sucrose, glucose, fructose, lactose, maltose, and invert sugar. Examples of sugar-like compounds include not only sugar syrups such as glucose syrup obtained by acidic hydrolysis or enzymatic decomposition of cellulose or starch, but also polyalcohols such as low molecular weight polyvinyl alcohol, sorbitol, mannitol and pental. Mention may be made of erythritol and sugar-form commercial formaldehyde condensation products, so-called formoses. The sugar and sugar-like compound can be used separately or in any desired mixture with each other.

Aqueous solutions of polymethylol compounds which can be used include, for example, phenol, urea and / or melamine, and / or water-soluble resole and / or novolac N-methylol compounds. N-methylol compounds are preferred. It is possible to use individual polymethylol compounds and any desired mixtures of different polymethylol compounds. Other examples of polymethylol compounds are water-soluble aminoplastics resins and water-soluble casein / formaldehyde resins, urea methylol compounds having up to 4 methylol groups per molecule and their water-soluble precondensation products. There is a thing. Urea methylol compounds can also be derived from burette and higher condensation products of urea.
Water-soluble melamine / methylol compounds and water-soluble methylol compounds of commercially available melamine resins, such as those containing 3 to 6 methylol groups in one molecule and precursors thereof are suitable. It is also possible to use dispersions of melamine resins. Particularly suitable methylol compounds are those which promote the flame resistance of the polyurethane / polyureas produced.

Aqueous solutions of sugars and polymethylol compounds also contain less than 50% by weight of water, especially 20 to 45% by weight.
It is preferable to include. The sugar solution can be used, for example, as a mixture with the aqueous composition of the amine adduct of the acidic metal salt, for example in the form of a premix. Optionally a base already present in the system (eg ethanolamine, triethanolamine, ammonia or an alkali metal hydroxide) is added to bring the pH of such a premix to 5.5-8.
It can also be adjusted to.

In one particular embodiment, the preparation of the polyurethane / polyureas according to the invention is carried out, for example, by adding the solid sugar and / or polymethylol compound to an aqueous solution of an amine adduct of an acidic metal salt, for example at 10-100 ° C. Preferably 20
It is carried out by preparing an aqueous solution of a sugar and / or a polymethylol compound in-situ by dissolving at ~ 60 ° C.

If polymethylol compounds are (also) used, it is advantageous to introduce them separately into the reaction zone immediately before the reaction or to mix them with one or more starting components.

If urea is used, it is convenient to dissolve it in the aqueous composition of the amine adduct of the acidic metal salt, optionally at elevated temperature, preferably 30-95 ° C.

For example, 0.5 to 250% by weight, preferably 1 to 100% by weight of sugar, and / or 0 to 70% by weight, preferably 0.1, of the amine adduct of the acidic metal salt.
-50% by weight of urea can be used.

Polyisocyanates which can be used are aliphatic, aromatic, aliphatic-aromatic, modified polyisocyanates such as are used industrially in the production of polyurethane / polyureas. Suitable polyisocyanates are those of the commercially available liquid MDI grade, for example based on the aniline / formaldehyde condensation products, tolylene diisocyanates, and their modified products, which preferably have a high boiling point.

Polyols which can be used are, in particular, the aliphatic alkoxylation products of ammonia and amines which are customarily used for preparing polyurethane / polyureas, preferably containing a tertiary nitrogen. Preferred alkoxylation products are ethoxylation or propoxylation products, preferred amines are those containing 1 to 12, preferably 1 to 8, amino groups in a molecule. The alkoxylation product has an OH number of, for example, higher than 50, preferably higher than 300. Specific compounds are mono-, di- and triethanolamines, tripropanolamines and ethoxylated and propoxylated products of ammonia or ethylenediamine, polyethylene polyamines and mixtures thereof. Triethanolamine, and OH number is 300
Particularly preferred is ˜600 of its propoxylated product. The polyols mentioned here are generally basic.

In addition to the polyisocyanates, polyols and the components used in the production of the polyurethane / polyureas according to the invention, other components known per se in polyurethane chemistry can optionally be added. Such other ingredients can be, for example, modified or non-basic polyols, stabilizers, cell regulators, emulsifiers, activators, carboxylic acids, pH regulators, and / or additives.

Modified polyols which can be used are polymeric polyol dispersions, dispersions of PHD, polyureas and aminoplastics / polyols, polyether polyols having properties other than those mentioned above, for example polyols of different raw materials, other OH. Valent and / or other reactive groups,
For example, polyols having amino, carboxyl and / or sulfoxyl groups. Sugar polyol, ester polyol, polyester polyol, polyether amine and / or polyester amine having a molecular weight of, for example, 62 to 12,000 and an OH value of, for example, 10 to 80.
Those of 0, preferably 30 to 600 can also be used.

Stabilizers which can be used are, for example, polyether /
As polysiloxanes, as in normal polyurethane chemistry, surfactants can be considered as emulsifiers and, for example, tertiary amines and organometallic compounds can be considered as activators.

The carboxylic acids can be mono- and polycarboxylic acids, for example having 1 to 180 carbon atoms, preferably 1 to 60 carbon atoms and being liquid at room temperature. Examples of carboxylic acids are formic acid, acetic acid, alkylacetic acids, and phenylacetic acid, suitable acids being the acids of permanent natural acids such as oleic acid, ricinoleic acid, linseed oil fatty acid, isostearic acid, tall oil fatty acid, soybean oil. Fatty acids, fish oil fatty acids, rapeseed oil fatty acids, synthetic fatty acids, and dimer acids, trimer acids and polymer fatty acids obtained from the above fatty acids. A fatty acid mixture containing oleic acid and oleic acid is particularly preferred. These fatty acids can be used in whole or in part in the form of salts, for example sodium, potassium and / or alkanolamine salts. Although less preferred embodiments, halogenated fatty acids may be used, such as chlorinated, brominated, and / or iodinated oleic acid, ricinoleic acid, and / or flaxseed oil fatty acid. Although it is not absolutely necessary to add a carboxylic acid, carboxylic acids are often preferred because they facilitate foam formation, especially foams that produce fine cells. The proportion of carboxylic acid in the total reaction mixture is, for example, 0 to 25% by weight. This ratio is 1
Preferably it is 10% by weight. If necessary, the pH can be adjusted by using an acid, amine or alkali.
Orthophosphoric acid, ethanolamine and sodium hydroxide are preferred. It is preferred to adjust the pH of the reaction mixture to 5.5-8, particularly preferably 6.5-7.5.

The additives can be of a wide variety. For example, foaming agents, fillers and / or sugars and / or polymethylol compounds in forms other than aqueous solutions. Blowing agents which can be used are, for example, pentane, cyclopentane, fluorocarbon, which are usually used in polyurethane chemistry,
These are halogenated fluorocarbons, dimethyl ether, and others. The proportion of blowing agent in the total reaction mixture is, for example, 0 to 20% by weight. 3 to 10% by weight is suitable.

Fillers which can be used are, for example, hydrophobic natural oils such as rapeseed oil, paraffin oil and / or paraffin wax, and polyisobutylene, polysiloxanes, polyolefins and / or fluorinated polymers.

The filler may have an additional flameproofing effect, in which case the filler may be, for example, a solid material, an expanded material, an expandable material, a liquid, a powder material, or beads or hollow beads. Material in the form of. Examples thereof include expandable graphite, expandable mica, silicates, glasses, borosilicates, and non-expanding additives that provide flame retardant properties, such as urea resin, melamine or phenolic resin powders, phosphate esters, Aqueous solutions or powders of phosphorus-containing polyols, amines of phosphoric acid or boric acid, salts of alkali metals, alkaline earth metals, zinc and / or aluminum (eg ammonium phosphate, ammonium polyphosphate, borax, zinc borate, ethanolamine salts of boric acid). , And primary and / or ammonia, monoethanolamine, sodium, aluminum and / or zinc
Or secondary orthophosphate, and / or US Pat.
414 374, No. 3 945 987 and No. 4 076 540), ethylenediamine phosphate, mono-, di-, and / or triethanolamine salts of orthophosphate, melamine, melamine phosphate,
Of dicyandiamide, burette, amide and / or ester of phosphoric acid, such as tricresyl phosphate, phenylalkyl phosphate, tris-trichloroethyl phosphate, ammonium chloride, ammonium bromide, amines and metal halides such as sodium bromide or polyalkylene polyamines. Hydrobromide, hydrobromide of triethanolamine, ortho-, meta-, pyro- or polyphosphoric acid, optionally in aqueous solution or salt form, hydrogen chloride, hydrogen bromide, colemanite, zinc borate, titanium dioxide. And / or magnesium and / or aluminum hydroxide. Halogen-free additive components are preferred.

Sugar and / or polymethylol compounds to be added as an aqueous solution according to the method of the invention, such as pentaerythritol, sugar, starch, paraformaldehyde,
Urea methylol compounds, phenolic resins and / or amine adducts of metal phosphates can additionally be added to the reaction mixture in solid form as fillers.

Generally, all components which are to be incorporated into the reaction mixture are introduced into the reaction zone either separately or, preferably, premixed, with the sugar solution, the polymethylol compound, the amine adduct of the acid metal salt and these components. Regardless of the water introduced with the above, a polyisocyanate having an equivalent value or more is used. The amount of this polyisocyanate is, for example, 1
It is 20 equivalent% or more, preferably 150 to 250 equivalent%.

The amine adduct of the acidic metal salt, the sugar and / or the polymethylol component is, for example, in an amount of more than 5% by weight,
An amount of preferably 25% by weight, particularly preferably 30 to 8
It can be introduced into the reaction mixture together in an amount of 0% by weight (but without blowing agent and filler).

When referring to the relative proportions of the raw material components in producing a polyurethane / polyurea according to the method of the present invention, it is often convenient to use weight ratios rather than stoichiometric proportions. For example, the reaction can be carried out in the following relative proportions.

(A) An amine adduct of an acidic metal salt, for example, 1% by weight or more, preferably 3 to 75% by weight, particularly 5 to 6%
5% by weight.

(B) Urea, for example 0 to 40% by weight, preferably 1 to 30% by weight.

(C) Total amount of sugar and polymethylol compound, for example 0.5 to 65% by weight, preferably 1 to 50% by weight, especially 10 to 40% by weight.

The sum of (a) + (b) + (c) is, for example, 25 to 75% by weight, preferably 40 to 65% by weight, and only one component of sugar and polymethylol compound is present. If both are present, the relative proportion of the two is any desired value.

(D) polyisocyanate, polyol,
The total amount of modified polyol, activator, and emulsifier, for example, 10 to 75% by weight, preferably 25 to 55% by weight. The amount of isocyanate here is given in equivalent% as described above.

(E) Carboxylic acid, for example 0 to 20% by weight, preferably 1 to 10% by weight.

(F) Additive (excluding foaming agent), for example, 60% by weight or less, preferably 0 to 50% by weight.

(G) Blowing agent, for example 0 to 20% by weight, preferably 3 to 10% by weight.

(H) Water, for example 1 to 15% by weight, preferably 3 to 9% by weight.

The combined value of components (a) to (h) is always 100% by weight.

It is generally advantageous to carry out the manufacturing process of the invention with heating. The temperature is, for example, 10 to 70 ° C., preferably 15 to 40 ° C., and heating can be carried out before and / or during and / or after combining the individual components. When using a furnace for heating,
The furnace can be operated, for example, at 30-100 ° C, preferably 65-95 ° C.

The process according to the invention can be carried out at standard pressure or above standard pressure with or without blowing agent. Depending on these parameters, a more or less foamed monolithic product or foam is obtained. Density is 1
It is preferable to produce a foam having a pore diameter of 0.01 to 3 mm at 5 to 500 g / l, particularly 18 to 50 g / l.

The production of the foam itself can be carried out by methods commonly used in the polyurethane foam industry. For example batch, continuous, high pressure, medium and low pressure multi-component mixing using nozzles or agitating mixing heads, casting, spraying, injection molding or double belt making, and open lid Alternatively, it is possible to use a method of foaming in a closed heated or unheated mold freely or in the mold without or with pressure.

Foams made according to the present invention may be packaged, for example,
It can be used for sound insulation, decoration, fitting, filters (especially air filters), insulation products and fire protection.

These products have improved flammability resistance and low fire loads.

Since the foams of the invention are produced in open cell form, these foams are optionally further plated and, for example, flame resistant materials, casting resins, lacquers, hydrophobizing agents, sterilizing agents,
It can be impregnated or coated with silicone oil, as well as added amine adducts of acid metal salts used in the preparation, mortar and / or plaster.

Foams made in accordance with the present invention may be used in various outer layers such as paper, glass woven gauze, metal fiber nets, organic fiber nets, woven fiber cloths, deposited fiber cloths, nonwovens, plastics, wood or metal. The film, plywood or sheet can be used to make a sandwich structure. Such foams also fill voids and can be used as fixing aids for building components, as acoustic barriers, as filters or packaging materials, and for impact protection.

Since most of these foams can be made with an open cell structure, they are suitable for the production of so-called vacuum panels. In this case the foam is fitted with an airtight coating or cover and a vacuum is applied. In this way an improved blocking effect is obtained.

The foam of the present invention can be machined, heat shock processed,
Welding, embossing or multi-dimensional molding and cutting can be performed. Depending on the degree of drying, the residual water content is 0.5-15% by weight over 120-200 ° C. Further, since it has a certain degree of thermoplasticity, it can be thermoformed. The foams of the present invention are also electroplatable, thermally compressible and sewn together.
Therefore, it has many uses as a semi-finished product.

The polyurethane / polyurea foams produced according to the invention, in particular the polyurethane / polyurea foams, show improved behaviour.

According to the invention, it is surprising that the behavior in case of fire is improved, since it is expected that additional organic materials will be used, which will result in further combustion gas loads. Aqueous solutions are often incompatible with polyisocyanates, and contain water and sugar and / or
Alternatively, a polymethylol compound introduces further OH groups which, in principle, can react with polyisocyanates and are expected to produce unfavorable changes in properties, but with sugar and / or Surprisingly, the addition of an aqueous solution of the polymethylol compound according to the process according to the invention does not have any effect on the foamability of the foam.

[0056]

EXAMPLES All proportions are by weight unless otherwise stated.

Description of raw material manufacturing method and laboratory combustion shaft test method (1) Phosphoric acid metal salt / amine adduct solution (solution AB /
1) (a) Dilute 2768 parts of 85% orthophosphoric acid with 660 parts of water. Then add 624 parts of aluminum hydroxide,
Stir at 90 ° C. for 30 minutes. A clear solution of acidic aluminum phosphate was obtained.

(B) 1600 parts of 741.6 parts of orthoboric acid
Dissolve in 1 part of monoethanolamine and add 2 more at 70 ℃
Stir with 4 parts of water to make a clear solution.

(C) Add two solutions obtained by this method to 8
Combined well and stirred well at 0 ° C. to obtain a clear solution of boron phosphate / aluminum ethanolamine salt.

The concentration of this solution is about 76% and is 20 ° C.
Has a density of 1.6 g / cm3 and a viscosity of 3000 mP
a. s.

In the following description, this solution is referred to as solution AB / 1.
And

(2) Metal Phosphate / Amine Adduct Solution (Solution AB / 2) (a) 183.2 parts of ethanolamine in a stirred vessel at 80 ° C. with a clear solution using 185.4 parts of orthoboric acid. Change to.

(B) 173.3 parts of 85% orthophosphoric acid are introduced at room temperature into the stirring vessel. 25 of ammonia
% Solution of 212.5 parts was added with stirring and the internal temperature was adjusted to 5
Keep at 0 ° C.

(C) 99.5 parts of 519.8 parts of 85% orthophosphoric acid
Reaction with 156 parts ammonium hydroxide at 5 ° C. gave a substantially clear solution of acidic metal phosphate. The solution was cooled to 70 ° C.

(D) At 50 ° C., the solution obtained in (b) is added to the solution obtained in (c) kept at 70 ° C. with sufficient stirring. This gives a substantially clear stirrable solution. The solution is stirred at 90 ° C. for 30 minutes. The temperature was then lowered to below 50 ° C. to obtain a stable pourable solution at room temperature.

(E) The solution obtained in (d) was adjusted to 80-90.
Mix with the solution obtained in (a) with vigorous stirring at ° C. Stirring is continued for another hour at 80-90 ° C. and the mixture is cooled with stirring. An almost transparent solution was obtained which was easily pourable at room temperature (viscosity 6000 mPa.s).
s). The solution of this metal phosphate / amine complex is hereinafter referred to as solution AB / 2.

(3) Metal Phosphate Complex (Solution AB / 3) The solution obtained by (2a) is added to the solution AB / 1 obtained in (1c) with stirring at room temperature. 80 ° C
At 30 ° C. for 30 minutes to obtain a clear solution of metal phosphate containing boron. Hereinafter this solution is referred to as AB / 3.

(4) Sugar solution Z / 1 A 75% aqueous solution of normal edible sugar (sucrose) was prepared.

(5) Sugar solution Z / 2 A commercially available 80% solution of so-called industrial glucose syrup. It is a mixture of many different sugars obtained enzymatically from starch.

(6) Solution of polymethylol compound M / 1 Ordinary commercial urea / formaldehyde resin [Plastopal ^(R)] which is hardly cross-linked.
BASF] aqueous solution of about 75%.

(7) Solution of polymethylol compound M / 2 Ordinary commercially available urea / formaldehyde resin [Madurit ^(R) HW] which is hardly cross-linked.
550, Casella], about 75% aqueous solution.

(8) Polymethylol Compound Solution M / 3 Ordinary Commercial Novolac Resin (Ruettgers)
75% aqueous solution of.

(9) Laboratory combustion shaft test method Specimen: cut from the center of the foamed product to be tested, the largest face having a rough finished surface. The dimensions are 2 x 20 x 5 cm. The test piece is dried at 80 ° C. for 24 hours or conditioned at room temperature and 65% relative humidity. Four specimens were used as the wall of the shaft structure (square, open cross section 3 × 3 cm) for each measurement.

Shaft structure: First, the edge length is 5 cm,
A shaft (hollow member) is made from a mesh of stainless steel wire having a height of 22 cm. Insert the test piece along the wall into this shaft to make a shaft with inner square dimensions of 3 x 3 cm and height of 20 cm. The wire mesh portion of the outer grip still extends 2 cm above the interior of the foam. The shaft made in this way is placed on a wire mesh with a 4.5 cm diameter hole cut from the center. Align the center of the shaft with this hole. A normal commercial natural gas burner with a 2.5 cm diameter ceramic perforated disk nozzle is placed in the center of the hole at a distance of 5 cm from the net and ignited. Fill out the gas and operate the burner to remove the bright area.
Adjust the air supply to produce a 5 cm cone flame. Burn for 30 seconds. When the foam ignites and burns during operation of the burner, a flame of readily combustible gas produced by pyrolysis was observed above the shaft.

Testing: The following parameters were then determined.

T1: Whether or not gas is burned due to such thermal decomposition and flame is generated.

T2: Is pyrolysis gas extinguished after the burner is ignited? If so, what time is it?

T3: 30 seconds after turning off the burner,
How long did the foam shaft continue to burn?

T4: Is the foam sometimes burned and partially or completely gone?

Each test was tested 5 times separately and the results were averaged.

When these tests are always carried out in the same way as in the examples below, these tests give reliable and reproducible relative data on the combustion properties of the foams tested. A control foam (obtained according to Example 1) was also used in each series of tests.

Example 1 (Control) Foam without the addition of sugar or polymethylol compounds 300 parts of solution AB / 1, 3 parts by weight of 50% aqueous sodium hydroxide solution, 25 parts of propylated trihydrate Ethanolamine (OH number 500), 12.5 parts oleic acid,
20 parts triethanolamine, 2 parts polyether /
The polysiloxane stabilizer and 30 parts of cyclopentane are premixed with vigorous stirring and immediately thereafter with vigorous stirring the usual commercial MDI = diphenylmethane 4,4'-diisocyanate [Desmodur ^{(R )} 44V20; Bayer]
Mix with 100 parts.

As soon as foaming begins, the mixture is placed in a box-shaped mold until the foaming ends and the foam is ready.
The foam is either dried (Test A) or conditioned (Test B). The obtained foam having fine pores uniformly distributed had a density of 21 g / l. A combustion shaft test was conducted and the following results were obtained.

Test A Test B T1 Yes, Strong Yes T2 No No T3 Within 30 seconds Less than 30 seconds T4 Completely absent Partially absent Example 2 Using the same method as Example 1, but solution AB / 1 Was used in place of AB / 2. The density of the obtained foam is 25 g /
It was l.

Test Results Test A Test B T1 Yes Yes Both are weaker than Example 1 T2 No No No T3 30 seconds 25 seconds T4 Partially lost No conclusions from this test when evaluated on a critical basis However, the behavior against fire is not satisfactory.

Example 3 (Control) The same method as in Example 1 was used, but using solution AB / 3 instead of solution AB / 1. A fine cell foam having a density of 31 g / l was obtained.

Test Results Test A Test B T1 Yes Yes T2 No No T3 20 seconds 15 seconds T4 Partially lost Very little Example 4 The same method as in example 1 was used, but with solution AB / 1 instead of solution AB / 1. A mixture of 80% AB / 1 and 20% Z / 1 was used. A fine cell foam having a density of 22 g / l was obtained.

[0088] Example 5 The same method was used as in Example 1, but instead of solution AB / 1, a mixture of solution AB / 2 70% and Z / 2 30% was used. A fine cell foam having a density of 23 g / l was obtained.

[0089] Example 6 The same method was used as in Example 1, but instead of solution AB / 1, a mixture of solution AB / 3 70% and Z / 2 30% was used. A fine cell foam having a density of 28 g / l was obtained.

[0090] Example 7 The same method was used as in Example 1, but instead of solution AB / 1, a mixture of solution AB / 2 of 60% and M / 3 of 40% was used. A fine cell foam having a density of 29 g / l was obtained.

[0091] Example 8 The same method was used as in Example 1, but instead of solution AB / 1, a mixture of solution AB / 3 60% and M / 1 40% was used. A fine cell foam having a density of 27 g / l was obtained.

[0092] Example 9 The same method was used as in Example 1, but instead of solution AB / 1, a mixture of solution AB / 1 of 50% and M / 2 of 50% was used. A fine cell foam having a density of 27 g / l was obtained.

[0093] Example 10 The same method was used as in Example 1, but instead of solution AB / 1, a mixture of solution AB / 1 50%, urea 10%, solution M / 2 40% was used. A fine cell foam having a density of 24 g / l was obtained.

[0094] Example 11 The same method was used as in Example 1, but instead of the sodium hydroxide solution 3 parts of 85% phosphoric acid were used. Density is 34g
A foam with fine cells of 1 / l was obtained.

[0095] Example 12 The same method was used as in Example 1, but instead of solution AB / 1, solution AB / 1 was 50%, solution M / 2 was 30%, and solution Z was
A mixture of 20% / 2 was used. A fine cell foam having a density of 26 g / l was obtained.

[0096] Example 13 The same method was used as in Example 1, but 50 parts of dry expanded graphite (expandable graphite, commercial product) were mixed in with the polyisocyanate. An apparently uniform foam having a density of 38 g / l was obtained.

[0097] Compared with Examples 1 to 3, Examples 4 to 13 show that the combustion behavior of the foams made according to the method of the invention is clearly improved.

Example 14 185 parts of orthoboric acid and 429 g of sugar cane sucrose are dissolved in 1530 parts of solution AB / 1 at 80 ° C.
The solution was cooled and the same method was used as for solution AB / 1 in Example 1, but 3 parts of monoethanolamine were added instead of sodium hydroxide. A fine cell foam having a density of 30 g / l was obtained, which was mechanically tougher than the foam of Example 4.

[0099] Example 15 Dry sheets of foam made according to Examples 4-13 are heat-sealed in a polyamide / polyvinylidene chloride composite film and vacuum is applied to obtain a vacuum barrier member with advantageous burn resistance. To be

Example 16 The foams made according to Examples 8-13 were used to seal the wall and wire ducts against fire. Impregnation of these foams with a dilute solution of AB / 1 or melamine resin has been found to be particularly effective.

Example 17 Cut sheets, both (a) not coated with the films made in Examples 8-13 and (b) having a surface with an anti-acoustic coating, are both combustion resistant. It becomes a sound blocking member having.

Example 18 Sheets made from the foams obtained in Examples 8 to 13 were made of metal foil, woven fiber cloth, nonwoven cloth, paper, cardboard, compressed chipboard, plywood, synthetic resin, bitumen and plaster. Processed separately to make a sandwich structure. A lightweight barrier structure was obtained with a particularly favorable behavior on combustion.

Example 19 The foams made in Examples 4-7 were plated by conventional methods, initially without electricity and then electrically. A semi-finished product was obtained which was thermally compressible at 100-200 ° C., deformable, embossable, severable and sawable at room temperature.

The above description of the present invention is not intended to limit the present invention merely for purposes of illustration. It should be appreciated that various modifications can be made without departing from the spirit and scope of the invention.

The main features and aspects of the present invention are as follows. 1. Formula _{A 1~3 B 0~12 P 3~9 N 4~12} M 0~9 xH 2 O (I) where Shikichu A aluminum to the mixture of polyisocyanate and polyol, magnesium, from the group consisting of calcium and zinc Represents at least one hydroxide or oxide of a selected metal, B represents orthoboric acid, P represents an acid containing phosphorus, N represents at least one of amine or ammonia, and M represents an alkali metal. A method for producing a flame-resistant halogen-free polyurethane / polyurea from polyisocyanates and polyols by adding an amine adduct of an acidic metal salt, which represents a hydroxide, and x represents an integer of 0 to 90. An improved method of adding an aqueous solution of at least one sugar or polymethylol compound to the mixture.

2. The method of claim 1 further comprising adding urea to the mixture.

3. The adduct has the formula _{A 2~3 B 3~9 P 6 N 6~9} M 0~5 xH 2 O (II) where Shikichu A represents aluminum hydroxide, B represents ortho boric acid, P is ortho A phosphoric acid, N represents an alkanolamine, M represents a sodium or potassium hydroxide, and x represents an integer of 6 to 36.
The method described in the section.

4. Sugars are sugar syrups such as triose, tetrose, pentose, carbohydrates, dextrin, dextran, saccharose, glucose, fructose, lactose, maltose, invert sugar, cellulose or starch obtained by acidic hydrolysis or enzymatic decomposition of glucose syrup. , Polyalcohols and mixtures thereof, the polymethylol compound being phenol, urea and / or melamine, and / or water-soluble resole, Novolac N-methylol compound, water-soluble aminoplastics resin, water-soluble. -Derived casein / formaldehyde resins, derived from urea methylol compounds with up to 4 methylol groups per molecule, their water-soluble precondensation products, and higher condensation products of burette and urea The method of the claim 1 wherein is selected from the group consisting of hydrogen methylol compounds.

5. The amine adduct of the acidic metal salt of formula (I) is added as an aqueous composition containing less than 50% by weight of water, and the aqueous solution of the sugar or polymethylol compound has a water content of less than 50% by weight. The method described.

6. Regarding amine adducts of acidic metal salts,
A method according to claim 2 wherein 0.5-250% by weight sugar or polymethylol compound and 90-70% by weight urea are added.

7. The mixture is an amine adduct of an acidic metal salt of formula (I): greater than 1% by weight, urea: 0-40% by weight, sugar or polymethylol compound: 0.5-65.
% By weight, polyisocyanates, polyols, modified polyols, activators, emulsifiers total up to 75% by weight,
Here, the amount of polyisocyanate is larger than its equivalent value regardless of the amount of sugar solution, polymethylol compound, amine adduct of acidic metal salt, metal salt, and water introduced accompanying these components. , Carboxylic acid: 0 to 20% by weight, additive: less than 60% by weight, foaming agent: 0 to 2
0% by weight, water: 1 to 15% by weight, wherein the total sum is 100% by weight.

8. Polyurethane / polyurea has a density of about 1
A method according to claim 1 in the form of a foam of 5 to 500 g / l.

9. A foam produced by the method described in the above item 1.

10. A packaging material, a sound insulating material, a decoration material, a mounting material, a filter material, a heat insulating material or a flameproof material, which is made of the foam according to the above-mentioned item 9.

11. Paper, glass fiber cloth, metal fiber cloth, organic fiber cloth, woven fiber cloth, deposited fiber cloth, non-woven fabric or plastics, film of wood or metal, outer layer made from plywood or sheet, and its outside as filler A foam made by the method according to claim 1 sandwiched between layers, for filling voids, as a fixing aid for building members, as an acoustic barrier, as a filter, as a packaging material or impact resistant. Sandwich products used as materials.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09K 21/14 B65D 81/04 C4 (72) Inventor Gerd Japs Germany 51519 Odenthal Bingenjier Arkamp 25

Claims (4)

[Claims] 1. A mixture of a polyisocyanate and a polyol having the formula A _1-3 B _0-12 P _3-9 N _4-12 M _0-9 xH ₂ O (I) wherein A is aluminum, magnesium, calcium and Represents at least one hydroxide or oxide of a metal selected from the group consisting of zinc, B represents orthoboric acid, P represents an acid containing phosphorus, N represents at least one of amine or ammonia, M represents an alkali metal hydroxide, x represents an integer of 0 to 90, and an amine adduct of an acidic metal salt is added, and a flame-free polyurethane / polyurine having flame resistance from polyisocyanate and polyol is added. A method for producing urea, further comprising adding an aqueous solution of at least one sugar or polymethylol compound to the mixture. 2. A foam produced by the method according to claim 1. 3. A packaging material, a sound insulating material, a decorative material, a mounting material, a filter material, a heat insulating material or a flameproof material, which is made of the foam according to claim 2. 4. An outer layer made of paper, glass fiber cloth, metal fiber cloth, organic fiber cloth, woven fiber cloth, laid fiber cloth, non-woven fabric or plastics, wood or metal film, plywood or sheet, and Filling voids comprising a foam produced by the method of claim 1 sandwiched between its outer layers as a filling material, as a fixing aid for building members, as an acoustic barrier, Sandwich products used as filters, packaging materials or impact resistant materials.